Apparatus for measuring electrochemical potentials



July 17, 1951 E. L. GAMBETTA 2,550,857

APPARATUS FOR MEASURING ELECTROCHEMICAL POTENTIALS Filed June 11, 1946 3 Sheets-Sheet l 20 T il Z "Mi 1mm Ill a? IMHHIIIH lii ih .36 E R Q WOR/VEY y 1951 E. L. GAMBETTA 2,560,857 APPARATUS FOR MEASURING ELECTROCHEMICAL POTENTIALS Filed June 11. 1946 5 Sheets-Sheet 2 l 1 70 f 7.5 I

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APPARATUS FOR MEASURING ELECTROCHEMICAL POTENTIALS Filed June 11, 1946 3 Sheets-Sheet 5 4!- Q m m A w Patented July 17, 1951 APPARATUS FOR MEASURING ELECTRO- CHEMICAL POTENTIALS Emmanuel Lon Gambetta, Saint-Mande, France, assignor to Giodvad Grell, New York, N. Y.

Application June 11, 1946, Serial No. 675,846 In France June 13, 1945 6 Claims.

The present invention relates to methods and devices for measuring or checking potential differences on the zero method principle, and it is more especially, although not exclusively concerned, among these methods and apparatus,

with those relating to physico-chemical potentiometry and other fields of application in which small potential differences are brought into play.

Its object is to provide a method and device of this kind which are better adapted to meet the requirements of practice than those used for the same purposes up to the present time and in particular which are simpler, more sensitive and more accurate, while reducing and simplifying the operations to be performed for obtaining the desired measurements.

Other objects of my invention will result from the following detailed description of some specific embodiments thereof with reference to the accompanying drawings, given merely by way of example, and in which:

Fig. 1 is a diagrammatical view of an apparatus of the kind with which the invention is concerned, made according to the prior art;

Fig. 2 is a similar view of an apparatus of this kind made according to my invention for determining the value of a fixed potential X;

Fig. 3 is a diagrammatical view of a practical embodiment of such an apparatus;

Fig. 4 shows, in developed view, the cylindrical surface of the commutator of the apparatus of Fig. 3;

Fig. 5 is a diagrammatical view of an apparatus made according to the invention for checking the value of a variable potential difference a: with reference to a given potential difference V;

Fig. 6 shows a practical embodiment of an apparatus made on the principle disclosed by Fig. 5;

Fig. 7 is a developed view of the cylindrical surface of the commutator of the apparatus of Fig. 6;

Fig. 8 is a diagrammatical view of a modification of the apparatus of Fig. 5;

Fig. 9 similarly shows a simplification of the apparatus of Fig. 8;

Fig. 10 shows a practical embodiment of an apparatus according to Fig. 9;

Fig. 11 is a developed view of the cylindrical surface of the commutator of the apparatus of Fig. 10.

Fig. 12 is a diagrammatic view of an electrostatic amplifying device to be used in connection with my apparatus.

Fig. 13 diagrammatically illustrates the successive'connections between elements of my apparatus.

My invention is especially concerned with the measurement or checking of small potential differences, for instance for chemical analysis, industrial titrimetry (concentration measurements) electrochemical potential measurements, accuarte measurement of low potentials, and so on.

Up to the present time, these measurements were performed through apparatus of the kind diagrammatically illustrated by Fig. 1. The apparatus of Fig. 1 includes a potentiometric device including for instance a bridge arrangement, with a resistant and calibrated wire I connected to the terminals 2 and 3 of a direct current source 4. Terminal 2 is also connected to one of the central terminals, 5 of a double throw switch 6, the other central terminal, 5 of which is connected, through the interposition of a zero indicating apparatus l (galvanometer, electrometer, etc.) with a contact 8 slidable along wire I. The movable arms of switch 6 can be applied either on contacts 9 9 connected to the respective terminals of a standard source of electromotive force W or on contacts H H between which is applied the potential difference X to be measured, for instance that existing between two electrodes I2 and I3 extending into a solution contained in a vessel 1 4.

If N and N are the positions of sliding contact 8 for which instrument I gives a zero reading when switch 6 is connected with contacts 9 -4 and ll l l respectively, the value of potential difference X is:

In many cases, it is desired to measure a vari able potential it. For instance, for potentiometric chemical titration of a solution present in vessel l4, the value to be measured is the difference between the reference potential of an electrode l2 and the potential of an electrode l3, variable as a reagent of known concentration is being introduced into vessel [4. In this case, a reference potential V is chosen and the measurement to be made is that of the difference V-a: between this reference potential and the variable potential 0:.

The known method above mentioned compels the operator to act on switch 6 and sliding contact 8 in addition to the operations he is to perform chemical volumetry (addition of reagent, stirring of the solutions in vessel l 4, etc.). Furthermore, when it is necessary to make use, as electrode 13, of a glass electrode, which considerably increases the internal resistance of the cell, the

3 method is of low sensitivity and an amplifier must be used, which further compels the operator to proceed to frequent readjustments.

All these drawbacks are avoided, according to the present invention, by causing the difference between a reference potential V (either fixed or adjustable) and the potential to be measured (either a fixed potential X or a variable potential .1: the variations of which are to be followed) to charge a condenser, and subsequentlydischarging this condenser (possibly after amplification of the charge thereof, for instance through electrostatic means) into a measurement apparatus the indication of which permits of determining the momentary difference between the potential to be measured and the reference potential.

According to a feature of my invention, the various switching operations necessary for this purpose are automatically performed through suitable means, for instance a rotary switch operated at a suitable, but adjustable speed.

The apparatus shown by Figs. 2, 3 and 4 relate to the measurement of a constant potential difierence.

The arrangement of Fig. 2 is analogous to that of Fig, 1, but the central terminal of switch 6, instead of being connected directly to apparatus 1, is connected, through a switch IE, to a condenser IS. This condenser can be caused, by means of a switch to discharge into an indi cator apparatus (for instance a galvanometer l provided with its adjustable shunt winding 59).

According to a characte istic of my invention, if, for any reason (for instance because of the high resistance of the electrodes), the sensitive:- ness is too low, the charge of the condenser, is first amplified. through electrostatic means,.for instance a Kelvin replenisher 2t).

Thisapparatus (Fig. 12) includes two cylindrical parts'll and 72, metallic and insulated, carrying metallic springs l3 and it, said parts H and 72 being connected respectively both with the lower contacts of switch I5 and with the left hand side contacts of switch I! (Fig. ,2). Two

metallic insulated pieces and it are adapted to rotate about the common axis of pieces! I and 72. After condenser I6 hasbeen charged, and-in order to multiply this charge, the arms, of switch :5 are brought onto their lower contacts, and

switch ll is left open. Parts, 75-76 are then rotated. When rotating in the directionofthe arrow, conveyors l5 and it come into contact with two insulated springs Ti and 18, connected with each other; then they leave them before coming out from the zone of influence of indicators T1 and 12 connected with the terminals of measurement condenser it. Finally they come into contactwith springs 'lrand 14' and thesame cycle is repeated. The charge on armatures H and i2 increases as a eornetrical progression.

Referring to Fig. 13, condenser 16 is therefore charged (a), disconnected (b), connected with electrostaticamplifier-26 (c) for amplification of its charge, discharged into galvanometer l. (d), disconnected (e), short-circuited (I) then disconnected and again charged (a). All these operations are automatically controlled and. the electrostatic amplifier 2c is mechanically driven. Thus, condenser i6 is charged under the effect of the potential difference e that corresponds to the adjustment displacement of the sliding contact 8 of potentiometer I effected for balancing the electric bridge device, and said condenser is subsequently discharged into galvanometer l Aslongas-eis difierent from zero, thisgalvanometer is deflected. When there is no deflection in the galvanometer, the ratio of the potential that is measured to the standard potential W is equal to MN MN This result is obtained in a very simple manner, without requiring special observations, adjustments or calculations.

Figs. 3 and 4 givev an example of a practical construction of such an apparatus. In this embodiment of my invention, switches l5 and I! are combined together into a rotary commutator 2| which cooperates with brushes l5 I5 I5 and I1 respectively connected to the various circuits.

Rotary commutator 2! is driven at an adjustable speed bya small electric motor 22 which may also operate amplifier 2D. I

Rotary commutator H is provided with several conductor strips (Fig. 4) mounted on an insulating support 23. Conductor strip 2 1, which runs along most of the periphery of the com -v mutatonpermitsthe charging of condenser it, while the, feed circuit of apparatus 1 is shortcircu'ited by strip 25. The discharging of condenser It is producedby strip 26, a portion 26 of which short-circuits condenser I6 after the discharging thereof inorder to eliminate the influence of residual charges. The operator has merely to adjust the position of sliding contact 8 along wire I, while observing indicating apparatus 1 Owing to, the fact that sensitiveness is to a large degree independent of the resistance between electrodes, the measurements can be performed with apparatus including glass electrodes, which are the only electrodes that canbe used in certain mediums. I

The apparatus shownby Figs. 5 to 11 are intended for checking the difference between a variable potential and a fixed reference potential. Inthe important case of physico-chemical titrimetry this given potential, which characterizes a given proportion of a reagent, may be obtained in various Ways, for instance:

By the difference of potential between two points M and N of a wire 1 fed with current from a direct current source 4. in combination with an element. lilof fixedelectromotive force W (Figs. 2. to 4);

By asuitable potential difference V across the terminals of a suitable battery (Figs. 5 to 7) Ina special manner which is to be hereinafter describedgwhen the actual production of potential difference is, likely to involve difficulties or lack of accuracy.

Inthe case of Figs. 5, G and 7, condenser I 6 is charged and discharged in a manner analogous to that above described with reference to Figs. 2 to 4. But in this case, commutator i5 is fed with potential difference V-a:, value V being materialized by a battery 2? including two electrodes extendingin a suitable solution.

If difiiculties or inaccuracy may result from the actual provision of means for producing potential V, it is advantageous to make use of arrangements such as disclosed by Figs. 8 to 11.

In this case, three electrodes 29, 30 and 3| are provided in vessel, It, which contains the solution to be treated and into which the reagent is introduced by means of a nozzle 23.

In the embodiment of Fig. 8, electrode 29 is asccgssc' 5, constituted by a metal wire or strip immersed in a vessel closed at the bottom by a plug 32 of porous porcelain or fritted glass or by a leaking coclc or by a capillary tube, this vessel containing a solution of ions of the same metal as the electrode, this solution being of a given, and for instance very low, concentration. Electrode 31 is constituted in a similar manner, but the concentration of the solution of ions is different from that chosen for electrode 29 and, for instance, equal to that of the reagent. Electrode 30, which, in this example, is of the same metal as electrodes 28 and 3!, assumes, in the course of the titration operation, a potential intermediate between those of electrodes 29 and 3!.

Instead of being independent, the three electrodes in question may be mechanically interconnected while bein electrically insulated from one another and they may be mounted on an auxiliary support or on the wall of vessel it.

I may also, as shown by Fig. 9, combine clectrodes 29 and ti with vessel M by providing the latter with two tubular extensions separated by porous partitions 32 from the central portion of said vessel, said electrodes '28 and ti being partly immersed in solutions of diiierent concentrations, as above stated, contained in these tubular ex tensions.

The three electrodes are respectively connected to the three upper terminals of a switch 6 the central terminals of which are respectively con nected to two adjustable condensers lt and I6, whereas the lower terminals of this switch are connected, in the manner shown by the draw" ing and through an amplifier 26 (not always necessary but which is advantageously constituted as above described with reference to Fig. 12), with the switch ll of an indicator apparatus 1 (a galvanometer for instance). According to the position given to the movable element of switch 6 are successively charged, disconnected from each other, and reconnected in parallel with each other after reversing of one of them.

The final charge of the condenser equivalent to these two condensers H5 and Hi connected in parallel is equal to the difierence between the charges initially imparted to these condensers under the effect of the respective clifierences of potential between 29 and 30 on the one hand and 3d and 3! on the other hand. The final difference of potential across the terminals of this equivalent condenser is a linear function of the potential of so. According to the choice of the relative values of the capacities of these condensers I6 and E6 this difference of potential can be caused to become zero when the potential of 38} reaches the predetermined value V, thus specially constituting the reference potential V with the same accuracy as that with which the potentials of 29 and 3B are obtained.

Likewise, by operating switch ll, the feed circuit of galvanometer l is first shunted by a resistance equal to zero, then it is insulated and finally it can be connected to condensers T6 and I6 assembled in parallel, so as to permit the discharging thereof.

The arrangement of Fig. 9 may be simplified by connecting electrode iii! to the earth as shown by Fig. 9, so that-it can be touched by the operator. This permits of utilizing a double switch 6 between electrodes 2%, to, SI and condensers I6 I6 and a simple switch ll for controlling apparatus 1 Reference numeral 2%) designates an amplifier which may, if need be, be connected 6" with condensers I 6 and IE2 during their coupling' together.

Figs. 10 and 11 show a. practical embodiment of an apparatus made on the principle illustrated by Fig. 9 and including a rotary commutator.

Fig. 10' diagrammatically shows the connections between brushes 33 33 33 33 33 33 and condenser I6 electrode 3!, electrode 29, condenser I6 and the two terminals of the indicator apparatus 1 These brushes cooperate as in the case of Figs. 3 and 6 with a rotary commutator 2 l actuated by a small adjustable speed motor 22' and constituted by an insulating wall provided with conductor strips 3 3, 35, 3%, 3i

- and 38'.

When brushes 33 33 33 33 are in contact with strips 34 and s5, condensers it and it are simultaneously charged. These condensers are subsequently coupled together and discharged into the circuit of galvanometer l by means of strips 31 and 38, which are interconnected.

I thus obtain an operation which is basically analogous to that of the apparatus shown by Figs. 2 to 7. However, it should be noted that for checking a variable potential difference, the ap paratus of Figs. 5, 8 and 9 are particularly simple since they do not include a direct current source such as 4 nor an electric bridge with a wire such as l. Qnly an alternating current source is necessary, for operating the motor 22 of rotary commutator 2!. Such apparatus therefore introduce no special requirements except those inherentin chemical volumetry and it suinces, after having prepared electrodes 29 and 3E and adjusted the values of the capacities of condensers IG and [6 to start rotary commutator iii and to observe the indicator apparatus.

According to the speed of revolution of commutator 2|, both for measuring and for checking the potential differences to be considered, I obtain, for a low rotation, a series of ballistic dufiections which decrease before the point of equilibrium and increase beyond this point, the galvanometer or analogous indicator apparatus returning to zero between the impulses. On the contrary, for a quick rotation, I obtain a series of vibrations of the galvanometer about a deflecti'on which first increases, until the point of equilibrium is reached and then decreases be" .yond this point. The amplitudes of these vibrations are the lower as the inertia of the galvanometer is greater. The deflection of the galvanometer also becomes zero at the desired point.

The rate of addition of the reagent into vessel depends upon the speed to be obtained in the titration. It may be great at the beginning of the titration and slow near the presumed end thereof. The flow rate of the reagent is not imposed.

Owing to the fact that sensitiveness is mostly independent of the resistance between elec trodes, titration can be effected with glass electrodes, which are the only electrodes that can be utilized in certain liquids. When the circuits have a high resistance, the charging of the condensers may be slow, but if it is incomplete, the accuracy of the measurement remains unchanged, although the sensitiveness is reduced.

As the values of the capacities of the condensers can be modified (even during the operatlon), it is possible to vary the sensitiveness of the whole and the method and apparatus according to the invention can be applied to the general treatment of a solution containing several diiferent ions adapted to be acted upon by the same reagent, as this is the case, for instance, for a solution containing several halogen ions (Cl, Br, I) which can be precipitated by a reagent such as a salt of silver.

It should also be noted that the apparatus according to the present invention give stable and accurate measurements under all circumstances in view of the fact that they remain uninfluenced by perturbing actions such as an irregular diffusion of the reagent in vessel [4, an incomplete stirring obtained either by hand or by means of an auxiliary stirring means, which may be constituted by electrode 30 itself, etc.

The methods and apparatus according to my invention are well adapted for potentiometric chemical titrations for measuring ionic concentrations, either constant or variable by addition of a reagent in matters which may be either mineral or organic, either liquid or viscous, either good or bad conductors of electricity, in an oxidizing or reducing medium, either colored or not. They can also be applied to the measurement of an oxide reducing power, of a pH, for checking the quality of manufactured products, either on samples or in a continuous manner, for chemical separations or for adjusting concentrations inside given potential limits. Furthermore, when the rotary commutator is driven at high speed, the indications given by galvanometer T or any analogous apparatus can be recorded. On the other hand, these indications may be used for controlling relays for exerting any mechanical, electric or other action, either externally to the chemical system that is considered or inside this system (for instance for stopping the flow of reagent when the direction of deflection of the galvanometer tends to be reversed), or for operating luminous or sound electric signalling means.

In a. general manner, while I have, in the above description, disclosed what I deem to be practical and emcient embodiments of my invention, it should be well understood that I do not wish to be limited thereto as there might be changes made in the arrangement, disposition and form of the parts without departing from the principle of the present invention as comprehended Within the scope of the accompanying claims.

What I claim is:

1. A titrimeter which comprises, in combination, a main vessel adapted to contain the solution to be studied, an electrode in said vessel adapted to dip in this solution, two auxiliary half cells in capillary communication with said first mentioned vessel, two adjustable condensers, means for charging each of said condensers with the difference of potential between each auxiliary half-cell electrode, respectively and the first mentioned electrode, means for disconnecting said condensers from said electrodes, means for coupling said condensers together in series, an electrical measurement indicator, and means for discharging the whole of said two condensers thus coupled together into said indicator.

2. A titrimeter which comprises, in combination, a main vessel adapted to contain the solution to be studied, an electrode in said vessel adapted to dip in this solution, two auxiliary half cells in capillary communication with said first mentioned vessel, two adjustable condensers, means for temporarily connectin the armatures of each of said condensers with one of the auxiliary half cell electrodes and the first mentioned electrode respectively and subsequently disconnecting said condensers from said electrodes, means for coupling said condensers together in series, an electrical measurement indicator, and means for discharging the whole of said two condensers thus coupled together into said indicator.

3. A titrimeter which comprises, in combination, a main vessel adapted to contain the solution to be studied, an electrode in said vessel adapted to dip in this solution, two auxiliary half cells in capillary communication with said first mentioned vessel, two condensers, switch means for either temporarily connecting said electrode with the two corresponding respective armatures of the condensers and the two half cell electrodes with the remaining armatures or coupling said condensers together in series, an electrical measurement indicator, and switch means for discharging the whole of said two condensers thus coupled together into said indicator.

4. A titrimeter which comprises, in combination, a main vessel adapted to contain the solution to be studied, an electrode in said vessel adapted to ,dip in this solution, two auxiliary half cells in capillary communication with said first mentioned vessel, two condensers, switch means for either temporarily connecting said electrode with the two corresponding respective armatures of the condensers and the two half cell electrodes with the remaining armatures or coupling said condensers together in series, an electrical measurement indicator, switch means for discharging the whole of said two condensers thus coupled together into said indicator, and automatic means for successively and repeatedly operating said two switch means.

5. A titrimeter which comprises, in combination, a main vessel adapted to contain the solution to be studied, an electrode in said vessel adapted to dip in this solution, two auxiliary halfcells in capillary communication with said first mentioned vessel, two adjustable condensers, means for charging each of said condensers with the difference of potential between each auxiliary half-cell electrode, respectively, and the first mentioned electrode, means for disconnecting said condensers from said electrodes, means for coupling said condensers together in series, an electrical measurement indicator, means for .discharging the whole of said two condensers thus coupled together into said indicator and means for short circuiting said group of condensers.

6. A titrimeter according to claim 1 further including electrostatic means for multiplying the charge on the whole of said two condensers after their coupling together in series and prior to the discharging of the whole thereof into said indicator.

EMMANUEL LEON GAMBETTA.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,346,057 Reardon July 6, 1920 2,285,482 Wunsch June 9, 1942 2,361,295 Kanner et a1 Oct. 24, 1944 2,416,949 Perley et a1. Mar. 4, 1947 

